# Patent

## Title
Non-local plasma oxide etch

## Abstract

A method of etching exposed titanium oxide on heterogeneous structures is described and includes a remote plasma etch formed from a fluorine-containing precursor. Plasma effluents from the remote plasma are flawed into a substrate processing region where the plasma effluents may combine with a nitrogen-containing precursor such as an amine (N:) containing precursor. Reactants thereby produced etch, the patterned heterogeneous structures with high titanium oxide selectivity while the substrate is at elevated temperature. Titanium oxide etch may alternatively involve supplying a fluorine-containing precursor and a source of nitrogen-and-hydrogen-containing precursor to the remote plasma. The methods may be used to remove titanium oxide while removing little or no low-K dielectric, polysilicon, silicon nitride or titanium nitride.

## Background
CROSS-REFERENCES TO RELATED APPLICATIONS
This application claims the benefit of U.S. Prov. Pat. App. No. 61/738,855 filed Dec. 18, 2012, and titled “NON-LOCAL PLASMA OXIDE ETCH,” which is incorporated in its entirety herein by reference for all purposes.


BACKGROUND OF THE INVENTION
Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods for removal of exposed material. Chemical etching is used for a variety of purposes including transferring a pattern in photoresist into underlying layers, thinning layers or thinning Lateral dimensions of features already present on the surface. Often it is desirable to have an etch process which etches one material faster than another helping e.g. a pattern transfer process proceed. Such an etch process is said to be selective to the first material. As a result of the diversity of materials, circuits and processes, etch processes have been developed with a selectivity towards a variety of materials. However, there are few options tor selectively etching silicon nitride raster than silicon.
Dry etch processes are often desirable for selectively removing material from semiconductor substrates. The desirability stems from the ability to gently remove material from miniature structures with minimal physical disturbance. Dry etch processes also allow the etch rate to be abruptly stopped by removing the gas phase reagents. Some dry-etch processes involve the exposure of a substrate to remote plasma by-products formed from one or more precursors. For example, remote plasma excitation of ammonia and nitrogen id fluoride enables silicon oxide to be selectively removed from, a patterned substrate when the plasma effluents are flowed into the substrate processing region. Remote plasma etch processes have recently been developed to selectively remove a variety of dielectrics relative to one another. However, fewer dry-etch processes have been developed to selectively remove metals and/or their oxidation.
Methods are needed to selectively etch oxide layers from metal surfaces using dry etch processes.
BRIEF SUMMARY OF THE INVENTION
A method of etching exposed titanium oxide, on heterogeneous structures is described and includes a remote plasma etch formed from a flourine-containing precursor. Plasma effluents from the remote plasma are flowed into a substrate processing region where the plasma effluents may combine with a nitrogen-containing precursor such as an amine (N:) containing precursor. Reactants thereby produced etch the patterned heterogeneous structures with high titanium oxide selectivity while the substrate is at elevated temperature. Titanium oxide etch may alternatively involve supplying a fluorine-containing precursor and a source of nitrogen-and-hydrogen-containing precursor to the remote plasma. The methods may be used to remove titanium oxide while removing little or no low-K dielectric, polysilicon, silicon nitride or titanium nitride.
Embodiments of the invention include methods of etching a substrate in a substrate processing region of a substrate processing chamber. The substrate has an exposed titanium oxide region. The methods include flowing a fluorine-containing precursor into a remote plasma region fluidly coupled to the substrate processing region while forming a remote plasma in the remote plasma region to produce plasma effluents. The methods further include flowing a nitrogen-and-hydrogen-containing precursor into the substrate processing region without first passing the nitrogen-and-hydrogen-containing precursor through the remote plasma region. The methods further include etching the exposed titanium oxide region with the combination of the plasma effluents and the nitrogen-and-hydrogen-containing precursor in the substrate processing region.
Embodiments of the invention include methods of etching a substrate in a substrate processing region of a substrate processing chamber. The substrate has an exposed titanium oxide region. The methods include flowing ammonia and a fluorine-containing precursor into a remote plasma region fluidly coupled to the substrate processing region while forming a remote plasma in the remote plasma region to produce plasma effluents. The methods further include etching the exposed titanium oxide region with the plasma effluents in the substrate processing region.
Additional embodiments and features are set forth in part in the description that follows, and in part will become apparent to those skilled in the art upon examination of the specification or may be learned by the practice of the disclosed embodiments. The features and advantages of the disclosed embodiments may be realized and attained by means of the instrumentalities, combinations, and methods described in the specification.



BRIEF DESCRIPTION OF THE DRAWINGS
A further understanding of the nature and advantages of the disclosed embodiments may be realized by reference to the remaining portions of the specification and the drawings.
FIG. 1 is a flow chart of a titanium oxide selective etch process according to disclosed embodiments.
FIG. 2 is a flow chart of a titanium oxide selective etch process according to disclosed embodiments.
FIG. 3A shows a substrate processing chamber according to embodiments of the invention.
FIG. 3B shows a showerhead of a substrate processing chamber according to embodiments of the invention.
FIG. 4 shows a substrate processing system according to embodiments of the invention.



In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a dash and a second label that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the second reference label.
DETAILED DESCRIPTION OF THE INVENTION
A method of etching exposed titanium oxide on heterogeneous structures is described and includes a remote plasma etch formed from a fluorine-containing precursor. Plasma effluents from the remote plasma are flowed into a substrate processing region where the plasma effluents may combine with a nitrogen-containing precursor such as an amine (N:) containing precursor. Reactants thereby produced etch the patterned heterogeneous structures with high titanium oxide selectivity while the substrate is at elevated temperature. Titanium oxide etch may alternatively involve supplying a fluorine-containing precursor and a source of nitrogen-and-hydrogen-containing precursor to the remote plasma. The methods may be used to remove titanium oxide while removing little or no low-K dielectric, polysilicon, silicon nitride or titanium nitride.
In order to better understand and appreciate the invention, reference is now made to FIG. 1 which is a flow chart of a titanium oxide selective etch process according to disclosed embodiments. Prior to the first operation, the substrate is patterned leaving exposed regions of titanium oxide and regions of low-K dielectric which may be covered. The patterned substrate is then delivered into a substrate processing region (operation 110). A flow of nitrogen trifluoride is initiated into a plasma region separate from the processing region (operation 120). Other sources of fluorine may be used to augment or replace the nitrogen trifluoride. In general, a fluorine-containing precursor is flowed into the plasma region and the fluorine-containing precursor comprises at least one precursor selected from the group consisting of atomic fluorine, diatomic fluorine, nitrogen trifluoride, carbon tetrachloride, hydrogen fluoride and xenon difluoride. The separate plasma region may be referred to as a remote plasma region herein and may be within a distinct module from the processing chamber or a compartment within the processing chamber. The plasma effluents formed in the remote plasma region are then flowed into the substrate processing region (operation 125). At this point, the gas phase etch would have little selectivity towards titanium oxide and would have limited utility. However, a nitrogen-and-hydrogen-containing precursor is simultaneously flowed into the substrate processing region (operation 130) to react with the plasma effluents. The nitrogen-and-hydrogen-containing precursor is not passed through the remote plasma region (or any plasma formed outside the substrate processing region for that matter) and therefore is only excited by interaction with the plasma effluents.
The flow rate of the nitrogen-and-hydrogen-containing precursor may be between 0.5 and about 10 times the flow rate of the fluorine-containing precursor in disclosed embodiments. The flow rate ratio (nitrogen-and-hydrogen-containing precursor:fluorine-containing precursor) may preferably be between 1:1 and 5:1 or between 2:1 and 3:1 in embodiments of the invention. Nitrogen trifluoride (or fluorine-containing precursors in general) may be flowed into the remote plasma region at rates greater than or about 25 sccm, greater than or about 40 sccm, greater than or about 60 sccm or greater than or about 75 sccm in disclosed embodiments.
The patterned substrate is selectively etched (operation 135) such that the titanium oxide is removed at a significantly higher rate than the low-K dielectric. The reactive chemical species are removed from the substrate processing region and then the substrate is removed from the processing region (operation 145). Using the gas phase dry etch processes described herein, the inventors have established that etch selectivities of over 40:1 (titanium oxide etch rate: low-K dielectric etch rate) are possible. The titanium oxide etch rate exceeds the low-K dielectric etch rate by a multiplicative factor of about 50 or more, about 100 or more, about 150 or more, about 200 or more, or about 300 or more, in embodiments of the invention. Low-K dielectric materials may have a dielectric constant less than 3.5, less than 3.3, less than 3.1, or less that 3.0 in disclosed embodiments. Low-K dielectric materials may comprise or consist of silicon, carbon, oxygen and hydrogen.
The gas phase dry etches described herein have also been discovered to increase etch selectivity of titanium oxide relative to silicon (including polysilicon). Using the gas phase dry etch processes described herein, the inventors have established that etch selectivities of over 50:1 (SiO etch rate: Si etch rate) are possible. The titanium oxide etch rate exceeds the (poly)silicon etch rate by a multiplicative factor of about 50 or more, 100 or more, about 150 or more, about 200 or more, or about 300 or more, in embodiments of the invention.
The gas phase dry etches described herein have also been discovered to increase etch selectivity of titanium, oxide relative to silicon nitride (or titanium nitride). Using the gas phase dry etch processes described herein, the inventors have established that etch selectivities of over 50:1 TiO:SiN (or TiO:TiN) are possible. The titanium oxide etch rate exceeds the silicon nitride (or titanium nitride) etch rate by a multiplicative factor of about 50 or more, 100 or more, about 150 or more, about 200 or more, or about 300 or more, in embodiments of the invention.
The nitrogen-and-hydrogen-containing precursor may consist of nitrogen and hydrogen. The nitrogen-and-hydrogen-containing precursor may comprise an amine group, in embodiments of the invention, and may be referred to as an amine-containing precursor. An amine group is defined as having a nitrogen possessing a lone pair of electrons (denoted canonically N:). Therefore nitrogen-and-hydrogen-containing precursors include ammonia, methyl amine, ethylamine, diethylamine, methyl ethyl diamine and the like. Hydrogen-containing precursors may be simultaneously combined with the fluorine-containing precursor in the remote plasma region or prior to entry into the remote plasma region.
Reference is now made to FIG. 2 which is a flow chart of a titanium oxide selective etch process according to alternative disclosed embodiments. Prior to the first operation, the substrate is again patterned leaving exposed regions of titanium oxide and regions of low-K dielectric which may or may not be exposed. The patterned substrate is then delivered into a substrate processing region (operation 210). A flow of nitrogen tri fluoride is again initiated into a plasma region separate from the processing region (operation 220). The alternative sources of fluorine may again be used to augment or replace the nitrogen trifluoride. The separate plasma region may be referred to as a remote plasma region, as before, and may be within a distinct module from the processing chamber or a compartment within the processing chamber. Ammonia is also bowed into the remote plasma region (operation 225). This process is similar to the Siconi process with the exception of the exposed substrate materials and some deviations of process parameters as outlined herein. The plasma effluents formed in the remote plasma region are then flowed into the substrate processing region (operation 230).
The patterned substrate is selectively etched (operation 235) such that the titanium oxide is removed at a significantly higher rate than the low-K dielectric. The reactive chemical species are removed from the substrate processing region and then the substrate is removed from the processing region (operation 245). The selectivity embodiments and materials outlined with reference to FIG. 1 also apply to the process of FIG. 2. Substrate temperatures and process pressures also have been found to lie within the same embodiments which will be described shortly. On the other hand, the flow rate ratios may differ as follows. The flow rate of the ammonia may be between 1 and about 20 times the flow rate of the fluorine-containing precursor in disclosed embodiments. The flow rate ratio (ammonia:fluorine-containing precursor) may preferably be between 1:1 and 10:1 or between 3:1 and 7:1 in embodiments of the invention. The absolute How rate of the fluorine-containing precursor lie within the embodiments of the earlier example.
Without wishing to bind the coverage of the claims to theoretical mechanisms which may or may not be entirely correct, some discussion of possible mechanisms may prove beneficial. Radical-fluorine precursors are produced by delivering a fluorine-containing precursor into the remote plasma region. Applicants suppose that a concentration of fluorine ions and atoms is produced and delivered into the substrate processing region. Ammonia (NH3) in the plasma or unexcited amine-containing precursors may react with the fluorine to produce less reactive species such as ammonium bifluoride (NH4HF2) which travel into the substrate processing region. The delivery of hydrogen and fluorine as described herein allows the formation of solid byproducts (salts) of (NH4)2TiF6 at relatively low substrate temperatures (<70° C.). At higher substrate temperatures, the inventors suppose that the solid by-products are still formed on the exposed titanium oxide (TiO) surfaces but are concurrently removed during the etch process by maintaining the relatively high substrate temperature as outlined herein. By limiting the reactivity of the incoming chemical species, the inventors have found a way to remove titanium oxide while retaining silicon, titanium nitride, low-K dielectric material and silicon nitride on the patterned substrate surface. The selectivity combined with the lack of solid byproducts, make these etch processes well suited for removing titanium oxide structures from above delicate low-K dielectric materials while inducing little deformation in the remaining delicate structures.
During the etch processes described herein, the temperature of the substrate may be about 110° C. or more and about 400° C. or less, in disclosed embodiments. The temperature of the substrate may be above or about 70° C., above or about 90° C. above or about 110° C., above or about 130° C., above or about 150° C. or above or about 170° C. in disclosed embodiments. The temperature of the substrate may be below or about 400° C., below or about 350° C., below or about 325° C. or below or about 300° C. in disclosed embodiments. Any of the upper limits can be combined with any of these lower limits to form additional embodiments of the invention. In a preferred embodiment, the temperature of the substrate may be between 200° C. and 300° C. during the etching operation in embodiments of the invention.
The inventors have found that exposed interior components should be kept at elevated temperatures in order to avoid trapping the desirable etching agents (hypothesized to include ammonium bifluoride). Interior components include surfaces which come in contact with the etching agents which are formed in either configuration (see FIGS. 1-2 and associated discussion). Possible interior components will be discussed in greater detail in the exemplary equipment section, but may include a showerhead separating the substrate processing region from the remote plasma region. Interior components may include chamber walls, faceplates and dedicated ion suppression elements. Interior components may be kept above or about 70° C., above or about 90° C., above or about 110° C. or above or about 130° C. in disclosed embodiments during the etching operation. Maintaining an elevated temperature of between, for example, 130° C. and 170° C., has been determined to increase the etch rate of the substrate by ensuring adequate flow of neutral active etching species to the titanium oxide substrate surface.
A dedicated ion suppression element may be included in the remote plasma region in order to further control the ion density entering the substrate processing region. Reducing the ion concentration is believed to enable the high titanium oxide selectivities outlined earlier. The ion suppression element functions to reduce or eliminate ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may pass through the openings in the ion suppressor to react at the substrate.
The pressure in the substrate processing region may be above or about 0.1 Torr and less than or about 50 Torr, in disclosed embodiments, during the etching operation. The pressure may be above or about 0.1 Torr, above or about 0.2 Torr, above or about 0.5 Torr or above or about 1 Torr in disclosed embodiments. The pressure may be below or about 50 Torr, below or about 25 Torr, below or about 15 Torr or below or about 10 Torr in disclosed embodiments. Any of the upper limits can be combined with any of these lower limits to form additional embodiments of the invention. Additional titanium oxide selective etch process parameters are disclosed in the course of describing an exemplary processing chamber and system.
Exemplary Processing System
Processing chambers that may implement embodiments of the present invention may be included within processing platforms such as the CENTURA® and PRODUCER® systems, available from Applied Materials, Inc. of Santa Clara, Calif. Examples of substrate processing chambers that can be used with exemplary methods of the invention may include those shown and described in co-assigned U.S. Provisional Patent App. No. 60/803,499 to Lubomirsky et al, filed May 30, 2006, and titled “PROCESS CHAMBER FOR DIELECTRIC GAPFILL,” the entire contents of which is herein incorporated by reference for all purposes. Additional exemplary systems may include those shown and described in U.S. Pat. Nos. 6,387,207 and 6,830,624, which are also incorporated herein by reference for all purposes.
FIG. 3A is a substrate processing chamber 1001 according to disclosed embodiments. A remote plasma system (RPS 1010) may process the fluorine-containing precursor which then travels through a gas inlet assembly 1011. Two distinct gas supply channels are visible within the gas inlet assembly 1011. A first channel 1012 carries a gas that passes through the remote plasma system RPS 1010, while a second channel 1013 bypasses the RPS 1010. Either channel may be used tor the fluorine-containing precursor, in embodiments. On the other hand, the first channel 1002 may be used for the process gas and the second channel 1013 may be used for a treatment gas. The lid 1021 (e.g. a conducting top portion) and a perforated partition (showerhead 1053) are shown with an insulating ring 1024 in between, which allows an AC potential to be applied to the lid 1021 relative to showerhead 1053. The AC potential strikes a plasma in chamber plasma region 1020. The process gas may travel through first channel 1012 into chamber plasma region 1020 and may be excited by a plasma in chamber plasma region 1020 alone or in combination with RPS 1010. If the process gas (the fluorine-containing precursor) flows through second channel 1013, then only the chamber plasma region 1020 is used for excitation. The combination of chamber plasma region 1020 and/or RPS 1010 may be referred to as a remote plasma system herein. The perforated partition (also referred to as a showerhead) 1053 separates chamber plasma region 1020 from a substrate processing region 1070 beneath showerhead 1053. Showerhead 1053 allows a plasma present in chamber plasma region 1020 to avoid directly exciting gases in substrate processing region 1070, while still allowing excited species to travel from chamber plasma region 1020 into substrate processing region 1070.
Showerhead 1053 is positioned between chamber plasma region 1020 and substrate processing region 1070 and allows plasma effluents (excited derivatives of precursors or other gases) created within RPS 1010 and/or chamber plasma region 1020 to pass through a plurality of through moles 1056 that traverse the thickness of the plate. The showerhead 1053 also has one or more hollow volumes 1051 which can be filled with a precursor in the form of a vapor or gas (such as an amine-containing precursor) and pass through small holes 1055 into substrate processing region 1070 but not directly into chamber plasma region 1020. Showerhead 1053 is thicker than the length of the smallest diameter 1050 of the through-holes 1056 in this disclosed embodiment in order to maintain a significant concentration of excited species penetrating from chamber plasma region 1020 to substrate processing region 1070, the length 1026 of the smallest diameter 1050 of the through-holes may be restricted by forming larger diameter portions of through-holes 1056 part way through the showerhead 1053. The length of the smallest diameter 1050 of the through-holes 1056 may be the same order of magnitude as the smallest diameter of the through-holes 1056 or less in disclosed embodiments. In this way a fluorine-containing precursor may be flowed through through-holes 1056 in a dual-zone showerhead and a nitrogen-and-hydrogen-containing precursor may pass through separate zones (hollow volumes 1051) in the dual-zone showerhead, wherein the separate zones open into the substrate processing region but not into the remote plasma region.
Showerhead 1053 may be configured to serve the purpose of an ion suppressor as shown in FIG. 3A. Alternatively, a separate processing chamber element may be included (not shown) which suppresses the ion concentration traveling into substrate processing region 1070. Lid 1021 and showerhead 1053 may function as a first electrode and second electrode, respectively, so that lid 1021 and showerhead 1053 may receive different electric voltages. In these configurations, electrical power (e.g., RF power) may be applied to lid 1021, showerhead 1053, or both. For example, electrical power may be applied to lid 1021 while showerhead 1053 (serving as ion suppressor) is grounded. The substrate processing system may include a RF generator that provides electrical power to the lid and/or showerhead 1053. The voltage applied to lid 1021 may facilitate a uniform distribution of plasma (i.e., reduce localized plasma) within chamber plasma region 1020. To enable the formation of a plasma in chamber plasma region 1020, insulating ring 1024 may electrically insulate lid 1021 from showerhead 1053. Insulating ring 1024 may be made from a ceramic and may have a high breakdown voltage to avoid sparking. Portions of substrate processing chamber 1001 near the capacitively-coupled plasma components just described may further include a cooling unit (not shown) that includes one or more cooling fluid channels to cool surfaces exposed to the plasma with a circulating coolant (e.g., water).
In the embodiment shown, showerhead 1053 may distribute (via through-holes 1056) process gases which contain oxygen, hydrogen and/or nitrogen and/or plasma effluents of such process gases upon excitation by a plasma in chamber plasma region 1020. In embodiments, the process gas introduced into the RPS 1010 and/or chamber plasma region 1020 through first channel 1012 may contain fluorine (e.g. CF4, NF3 or XeF2). The process gas may also include a carrier gas such as helium, argon, nitrogen (N2), etc. Plasma effluents may include ionized or neutral derivatives of the process gas and may also be referred to herein as a radical-fluorine precursor referring to the atomic constituent of the process gas introduced.
Through-holes 1056 are configured to suppress the migration of ionically-charged species out of the chamber plasma region 1020 while allowing uncharged neutral or radical species to pass through showerhead 1053 into substrate processing region 1070. These uncharged species may include highly reactive species that are transported with less reactive carrier gas by through-holes 1056. As noted above, the migration of ionic species by through-holes 1056 may be reduced, and in some instances completely suppressed. Controlling the amount of ionic species passing through showerhead 1053 provides increased control over the gas mixture brought into contact with the underlying wafer substrate, which in turn increases control of the deposition and/or etch characteristics of the gas mixture. For example, adjustments in the ion concentration of the gas mixture can significantly alter its etch selectivity (e.g., TiO:low K dielectric etch ratios).
In embodiments, the number of through-holes 1056 may be between about 60 and about 2000. Through-holes 1056 may have a variety of shapes but are most easily made round. The smallest diameter 1050 of through-holes 1056 may be between about 0.5 mm and about 20 mm or between about 1 mm and about 6 mm in disclosed embodiments. There is also latitude in choosing the cross-sectional shape of through-holes, which may be made conical, cylindrical or a combination of the two shapes. The number of small holes 1055 used to introduce a gas into substrate processing region 1070 may be between about 100 and about 5000 or between about 500 and about 2000 in different embodiments. The diameter of the small holes 1055 may be between about 0.1 mm and about 2 mm.
FIG. 3B is a bottom view of a showerhead 1053 for use with a processing chamber according to disclosed embodiments. Showerhead 1053 corresponds with the showerhead shown in FIG. 3A. Through-holes 1056 axe depleted with a larger inner-diameter (ID) on the bottom of showerhead 1053 and a smaller ID at the top. Small holes 1055 are distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 1056 which helps to provide more even mixing than other embodiments described herein.
An exemplary patterned substrate may be supported by a pedestal (not shown) within substrate processing region 1070 when fluorine-containing plasma effluents arriving through through-holes 1056 in showerhead 1053 combine with ammonia arriving through the small holes 1055 originating from hollow volumes 1051. Though substrate processing region 1070 may be equipped to support a plasma for other processes such as curing, no plasma is present during the etching of patterned substrate, in embodiments of the invention.
A plasma may be ignited either in chamber plasma region 1020 above showerhead 1053 or substrate processing region 1070 below showerhead 1053. A plasma is present in chamber plasma region 1020 to produce the radical-fluorine precursors front an inflow of the fluorine-containing precursor. An AC voltage typically in the radio frequency (RF) range is applied between the conductive top portion 1021 of the processing chamber and showerhead 1053 to ignite a plasma in chamber plasma region 1020 during deposition. An RF power supply generates a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency.
The top plasma may be left at low or no power when the bottom plasma in the substrate processing region 1070 is turned on to either cure a film or clean the interior surfaces bordering substrate processing region 1070. A plasma in substrate processing region 1070 is ignited by applying an AC voltage between showerhead 1053 and the pedestal or bottom of the chamber. A cleaning gas may be introduced into substrate processing region 1070 while the plasma is present.
The pedestal may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate. This configuration allows the substrate temperature to be cooled or heated to maintain relatively low temperatures (from room temperature through about 120° C.). The heat exchange fluid may comprise ethylene glycol and water. The wafer support platter of the pedestal (preferably aluminum, ceramic, or a combination thereof) may also be resistively heated in order to achieve relatively high temperatures (Horn about 120° C. through about 1100° C.) using an embedded single-loop embedded heater element configured to make two full turns in the form of parallel concentric circles. An outer portion of the heater element may run adjacent to a perimeter of the support platter, while an inner portion runs on the path of a concentric circle having a smaller radius. The wiring to the heater element passes through the stem of the pedestal.
The substrate processing system is controlled by a system controller. In an exemplary embodiment, the system controller includes a hard disk drive, a floppy disk drive and a processor. The processor contains a single-board computer (SBC), analog and digital input/output boards, interface boards and stepper motor controller boards. Various parts of CVD system conform to the Versa Modular European (VME) standard which defines board, card cage, and connector dimensions and types. The VME standard also defines the bus structure as having a 16-bit data bus and a 24-bit address bus.
The system controller controls all of the activities of the etching chamber. The system controller executes system control software, which is a computer program stored in a computer-readable medium. Preferably, the medium is a hard disk drive, but the medium may also be other kinds of memory. The computer program includes sets of instructions that dictate the timing, mixture of gases, chamber pressure, chamber temperature, RF power levels, susceptor position, and other parameters of a particular process. Other computer programs stored on other memory devices including, for example, a floppy disk or other another appropriate drive, may also be used to instruct the system controller.
A process for depositing a film stack on a substrate or a process for cleaning a chamber can be implemented using a computer program product that is executed by the system controller. The computer program code can be written in any conventional computer readable programming language: for example, 68000 assembly language, C, C++, Pascal, Fortran or others. Suitable program code is entered into a single file, or multiple files, using a conventional text editor, and stored or embodied in a computer usable medium, such as a memory system of the computer. If the entered code text is in a high level language, the code is compiled, and the resultant compiler code is then linked with an object code of precompiled Microsoft Windows® library routines. To execute the linked, compiled object code the system user invokes the object code, causing the computer system to load the code in memory. The CPU then reads and executes the code to perform the tasks identified in the program.
The interface between, a user and the controller is via a flat-panel touch-sensitive monitor. In the preferred embodiment two monitors are used, one mounted in the clean room wall for the operators and the other behind the wall for the service technicians. The two monitors may simultaneously display the same information, in which case only one accepts input at a time. To select a particular screen or function, the operator touches a designated area of the touch-sensitive monitor. The touched area changes its highlighted color, or a new menu or screen is displayed, confirming communication between the operator and the touch-sensitive monitor. Other devices, such as a keyboard, mouse, or other pointing or communication device, may be used instead of or in addition to the touch-sensitive monitor to allow the user to communicate with the system controller.
The chamber plasma region or a region in an RPS may be referred to as a remote plasma region. In embodiments, the radical precursor (e.g. a radical-fluorine precursor) is created in the remote plasma region and travels into the substrate processing region to combine with an amine-containing precursor. In embodiments, the amine-containing precursor is excited only by the radical-fluorine precursor. Plasma power may essentially be applied only to the remote plasma region, in embodiments, to ensure that the radical-fluorine precursor provides the dominant excitation to the amine-containing precursor (e.g. ammonia).
In embodiments employing a chamber plasma region, the excited plasma effluents are generated in a section of the substrate processing region partitioned from a deposition region. The deposition region, also known herein as the substrate processing region, is where the plasma effluents mix and react with the amine-containing precursor to etch the patterned substrate (e.g., a semiconductor wafer). The excited plasma effluents may also be accompanied by inert gases (in the exemplary case, argon). The amine-containing precursor does not pass through a plasma before entering the substrate plasma region, in embodiments. The substrate processing region may be described herein as “plasma-free” during the etch of the patterned substrate. “Plasma-free” does not necessarily mean the region is devoid of plasma. Ionized species and free electrons created within the plasma region do travel through pores (apertures) in the partition (showerhead) but the amine-containing precursor is not substantially excited by the plasma power applied to the plasma region. The borders of the plasma in the chamber plasma region are hard to define and may encroach upon the substrate processing region through the apertures in the showerhead. In the case of an inductively-coupled plasma, a small amount of ionization may be effected within the substrate processing region directly. Furthermore, a low intensity plasma may be created in the substrate processing region without eliminating desirable features of the forming film. All causes for a plasma having much tower intensity ion density than the chamber plasma region (or a remote plasma region, for that matter) during the creation of the excited plasma effluents do not deviate from the scope of “plasma-free” as used herein.
Nitrogen trifluoride (or another fluorine-containing precursor) may be flowed into chamber plasma region 1020 at rates between about 25 sccm and about 200 sccm between about 50 sccm and about 150 sccm or between about 75 sccm and about 125 sccm in different embodiments. Amine-containing precursor may be flowed into substrate processing region 1070 at rates between about 25 sccm and about 200 sccm, between about 50 sccm and about 150 sccm or between about 75 sccm and about 125 sccm in different embodiments.
Combined flow rates of amine-containing precursor and fluorine-containing precursor into the chamber may account for 0.05% to about 20% by volume of the overall gas mixture; the remainder being carrier gases. The fluorine-containing precursor is flowed into the remote plasma region but the plasma effluents has the same volumetric flow ratio, in embodiments. In the case of the fluorine-containing precursor, a purge or carrier gas may be first initiated into the remote plasma region before those of the fluorine-containing gas to stabilize the pressure within the remote plasma region.
Plasma power can be a variety of frequencies or a combination of multiple frequencies. In the exemplary processing system the plasma is provided by RF power delivered to lid 1021 relative to showerhead 1053. The RF power may be between about 10 watts and about 2000 watts, between about 100 watts and about 2000 watts, between about 200 watts and about 1500 watts or between about 500 watts and about 1000 watts in different embodiments. The RF frequency applied its the exemplary processing system may be low RF frequencies less than about 200 kHz, high RF frequencies between about 10 MHz and about 15 MHz or microwave frequencies greater than or about 1 GHz in different embodiments. The plasma power may be capacitively-coupled (CCP) or inductively-coupled (ICP) into the remote plasma region.
Substrate processing region 1070 can be maintained at a variety of pressures during the flow of amine-containing precursor, any earner gases and plasma effluents into substrate processing region 1070. The pressure may be maintained between about 500 mTorr and about 30 Torr, between about 1 Torr and about 20 Torr or between about 5 Torr and about 15 Torr in different embodiments.
In one or mom embodiments, the substrate processing chamber 1001 can be integrated into a variety of multi-processing platforms, including the ProducerTM GT; CenturaTM AP and EnduraTM platforms available from Applied Materials, Inc. located in Santa Clara, Calif. Such a processing platform is capable of performing several processing operations without breaking vacuum. Processing chambers that may implement embodiments of the present invention may include dielectric etch chambers or a variety of chemical vapor deposition chambers, among other types of chambers.
Embodiments of the deposition systems may be incorporated into larger fabrication systems for producing integrated circuit chips. FIG. 4 shows one such system 1101 of deposition, baking and curing chambers according to disclosed embodiments. In the figure, a pair of FOUPs (front opening unified pods) 1102 supply substrate substrates (e.g., 300 mm diameter wafers) that are received by robotic arms 1104 and placed into a low pressure holding area 1106 before being placed into one of the substrate processing chambers 1108a-f. A second robotic arm 1110 may be used to transport the substrate wafers from the holding area 1106 to the substrate processing chambers 1108a-f and back. Each substrate processing chamber 1108a-f, can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CCD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation and other substrate processes.
The substrate processing chambers 1108a-f may include one or more system components for depositing, annealing, curing and/or etching a flowable dielectric film on the substrate wafer. In one configuration, two pairs of the processing chamber (e.g., 1108c-d and 1108e-f) may be used to deposit dielectric material on the substrate, and the third pair of processing chambers (e.g., 1108a-b) may be used to etch the deposited dielectric. In another configuration, all three pairs of chambers (e.g., 1108a-f) may be configured to etch a dielectric film on the substrate. Any one or more of the processes described may be carried out on chamber(s) separated from the fabrication system shown in different embodiments.
System controller 1157 is used to control motors, valves, flow controllers, power supplies and other functions required to carry out process recipes described herein. A gas handling system 1155 may also be controlled by system controller 1157 to introduce gases to one or all of the substrate processing chambers 1108a-f. System controller 1157 may rely on feedback from optical sensors to determine and adjust the position of movable mechanical assemblies in gas handling system 1155 and/or in substrate processing chambers 1108a-f. Mechanical assemblies may include the robot, throttle valves and susceptors which are moved by motors under the control of system controller 1157.
In an exemplary embodiment, system controller 1157 includes a hard disk drive (memory), USB ports, a floppy disk drive and a processor. System controller 1157 includes analog and digital input/output boards, interface boards and stepper motor controller boards. Various parts of multi-chamber processing system 1101 which contains processing chamber 1001 are controlled by system controller 1157. The system controller executes system control software in the form of a computer program stored on computer-readable medium such as a hard disk, a floppy disk or a flash memory thumb drive. Other types of memory can also be used. The computer program includes sets of instructions that dictate the timing, mixture of gases, chamber pressure, chamber temperature, RF power levels, susceptor position, and other parameters of a particular process.
As used herein “substrate” may be a support substrate with or without layers formed thereon. The patterned substrate may be an insulator or a semiconductor of a variety of doping concentrations and profiles and may, for example, be a semiconductor substrate of the type used in the manufacture of integrated circuits. Exposed “titanium oxide” of the patterned substrate may be predominantly TiO2 but may include concentrations of other elemental constituents such as nitrogen, hydrogen, carbon and the like. In some embodiments, titanium oxide films etched using the methods disclosed herein consist essentially of titanium and oxygen. Exposed “silicon oxide” of the patterned substrate is predominantly SiO2 but may include concentrations of other elemental constituents such as nitrogen, hydrogen, carbon and the like. In some embodiments, silicon oxide films etched using the methods disclosed herein consist essentially of silicon and oxygen. The term “precursor” is used to refer to any process gas which takes part in a reaction to either remove material from or deposit material onto a surface. “Plasma effluents” describe gas exiting from the chamber plasma region and entering the substrate processing region. Plasma effluents are in an “excited state” wherein at least some of the gas molecules are in vibrationally-excited, dissociated and/or ionized states. A “radical precursor” is used to describe plasma effluents (a gas in an excited state which is exiting a plasma) which participate in a reaction to either remove material from or deposit material on a surface. A “radical-fluorine precursor” is a radical precursor which contains fluorine but may contain other elemental constituents. The phrase “inert gas” refers to any gas which does not form chemical bonds when etching or being incorporated into a film. Exemplary inert gases include noble gases but may include other gases so long as no chemical bonds are formed when (typically) trace amounts are trapped in a film.
The terms “gap” and “trench” are used throughout with no implication that the etched geometry has a large horizontal aspect ratio. Viewed from above the surface, trenches may appear circular, oval, polygonal, rectangular, or a variety of other shapes. A trench may be in the shape of a moat around an island of material (e.g. a substantially cylindrical TiN pillar). The term “via” is used to refer to a low aspect ratio trench (as viewed from above) which may or may not be filled with metal to form a vertical electrical connection. As used herein, a conformal etch process refers to a generally uniform removal of material on a surface in the same shape as the surface, i.e., the surface of the etched layer and the pre-etch surface are generally parallel. A person having ordinary skill in the art will recognize that the etched interface likely cannot be 100% conformal and thus the term “generally” allows for acceptable tolerances.
Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosed embodiments. Additionally, a number of well known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.
Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.
As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a process” includes a plurality of such processes and reference to “the dielectric material” includes reference to one or more dielectric materials and equivalents thereof known to those skilled in the art, and so forth.
Also, the words “comprise,” “comprising,” “include,” “including,” and “includes” when used in this specification and in the following claims am intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups.

## Claims

1. A method of etching a substrate in a substrate processing region of a substrate processing chamber, wherein the substrate has an exposed titanium oxide region, the method comprising:
flowing a fluorine-containing precursor into a remote plasma region fluidly coupled to the substrate processing region while forming a remote plasma in the remote plasma region to produce plasma effluents;
flowing a nitrogen-and-hydrogen-containing precursor into the substrate processing region without first passing the nitrogen-and-hydrogen-containing precursor through the remote plasma region; and
etching the exposed titanium oxide region with the combination of the plasma diluents and the nitrogen-and-hydrogen-containing precursor in the substrate processing region.

2. The method of claim 1 wherein the patterned substrate further comprises a second exposed region selected from the group consisting of an exposed low-K dielectric region, an exposed silicon region, an exposed titanium nitride region or an exposed silicon nitride region and the selectivity of the etching operation (exposed titanium oxide region: second exposed region) is greater than or about 50:1.

3. The method of claim 1 wherein the nitrogen-and-hydrogen-containing precursor comprises an amine-containing precursor.

4. The method of claim 1 wherein the nitrogen-and-hydrogen-containing precursor comprises ammonia.

5. The method of claim 1 wherein the substrate processing region is plasma-free while etching the exposed titanium oxide region.

6. The method of claim 1 wherein the nitrogen-and-hydrogen-containing precursor is not excited by any remote plasma formed outside the substrate processing region.

7. The method of claim 1 wherein the fluorine-containing precursor comprises a precursor selected from the group consisting of atomic fluorine, diatomic fluorine, nitrogen trifluoride, hydrogen fluoride and xenon difluoride.

8. The method of claim 1 wherein the operation of flowing the fluorine-containing precursor duo the remote plasma region further comprises flowing a hydrogen-containing precursor into the remote plasma region.

9. The method of claim 1 wherein the fluorine-containing precursor flowed through through-holes in a dual-zone showerhead and the nitrogen-and-hydrogen-containing precursor passes through separate zones in the dual-zone showerhead, wherein the separate zones open into the substrate processing region but not into the remote plasma region.

10. The method of claim 1 wherein a temperature of the patterned substrate is greater than or about 70° C. and less than or about 400° C. during the etching operation.

11. The method of claim 1 wherein a temperature of the patterned substrate is greater than or about 150° C. and less than or about 350° C. during the etching operation.

12. A method of etching a substrate in a substrate processing region of a substrate processing chamber, wherein the substrate has an exposed titanium oxide region, the method comprising:
flowing ammonia and a fluorine-containing precursor into a remote plasma region fluidly coupled to the substrate processing region while forming a remote plasma in the remote plasma region to produce plasma effluents; and
etching the exposed titanium oxide region with the the plasma effluents in the substrate processing region.

13. The method of claim 12 wherein the patterned substrate further comprises a second exposed region selected from the group consisting of an exposed low-K dielectric region, an exposed silicon region, an exposed titanium nitride region or an exposed silicon nitride region and the selectivity of the etching operation (exposed titanium oxide region: second exposed region) is greater than or about 50:1.

14. The method of claim 12 wherein the substrate processing region is plasma-free while etching the exposed titanium oxide region.

15. The method of claim 12 wherein the nitrogen-and-hydrogen-containing precursor is not excited by any remote plasma formed outside the substrate processing region.

16. The method of claim 12 wherein the fluorine-containing precursor comprises a precursor selected from the group consisting of atomic fluorine, diatomic fluorine, nitrogen, trifluoride, hydrogen fluoride and xenon difluoride.

17. The method of claim 12 wherein the operation of flowing the fluorine-containing precursor into the remote plasma region further comprises flowing a hydrogen-containing precursor into the remote plasma region.

18. The method of claim 12 wherein the fluorine-containing precursor flowed through through-holes in a dual-zone showerhead and the nitrogen-and-hydrogen-containing precursor passes through separate zones in the dual-zone showerhead, wherein the separate zones open into the substrate processing region but not into the remote plasma region.

19. The method of claim 12 wherein a temperature of the patterned substrate is greater than or about 70° C. and less than or about 400° C. during the etching operation.

20. The method of claim 12 wherein a temperature of the patterned substrate is greater than or about 150° C. and less than or about 350° C. during the etching operation.